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ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 29, Number 10
BKCSDE 29(10)
October 20, 2008 |
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Title |
Selective Synthesis of a New Macropolycycle Containing One N-CH2-N Linkage
and Its Reaction with Cu2+ and Ni2+ Ions in Methanol
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Author |
Shin Geol Kang*, Jae Keun Kweon, Gyeong Rok Jeong, Uk Lee* |
Keywords |
Macrocycle, Nickel(II) complex, Copper(II) complex, Crystal structure, Methoxymethyl group
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Abstract |
The reaction of 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.01.18.07.12]docosane (L1) with formaldehyde in warm methanol yielded 3,14-dimethyl-2,6,13,17-tetraazatetracyclo[16.4.12.6.01.18.07.12]tricosane (L7) containing one 1,3-diazacyclohexane subunit. In methanol, L7 readily reacts with Cu2+ ion to form [CuL7(H2O)]2+ which is extremely inert against methanolysis. In the solution containing Ni2+ ion, however, L7 reacts with methanol to yield [NiL3]2+ (L3 = 2-(methoxymethyl)-5,16-dimethyl-2,6,13,17-tetraazatricyclo[16.4.01.18.07.12]- docosane), in which one N-CH2OCH3 pendant arm is appended. The copper(II) complex [CuL7(H2O)]- (ClO4)2·3H2O (I·3H2O) has a severely distorted trigonal bipyramidal coordination geometry with a 4-5-6-5 chelate ring sequence. The crystal structure of [NiL3](PF6)2·2H2O (IIb) shows that the N-CH2OCH3 pendant arm is not coordinated to the metal ion in the solid state. In various solvents (S), however, the nickel(II) complex exists as a mixture of [NiL3(S)]2+, in which the N-CH2OCH3 group as well as S is coordinated to the metal ion, and [NiL3]2+.
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1905 - 1910 |
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